Method of producing 1,8-naphthaldehyde monocarboxylic

ABSTRACT

A method of producing 1,8-naphthaldehyde monocarboxylic acid, characterized in that acenaphthylene is ozonized in the medium of a lower aliphatic alcohol, or in a mixture of a lower aliphatic alcohol with water, or in a mixture of an aliphatic ketone with water, in the presence of an alkaline earth metal hydroxide. The resulting reaction mass is treated with hydrochloric acid, the formed 1,8-naphthaldehyde monocarboxylic acid is separated from the alkaline earth metal hydroxide and washed to remove the traces of hydrochloric acid.

United States Patent 91 Menyailo et al.

[ 51 Apr. 17, 1973 [5 METHOD OF PRODUCING 1,8-

NAPHTHALDEHYDE MONOCARBOXYLIC [73] Assignee': Nauchno-lssledovatclsky institut sinteticheskikh spirtov, Moscow,

U.S.S.R.

[22] Filed: July 24, 1970 [21] Appl.No.: 58,209

'52 us. (:1. ..260/523 1R, 260/610 R [51] Int. Cl. ..C07c 51/34 [58] Field of Search ..260/523 R, 610 R [5 6] References Cited UNITED STATES PATENTS 2,966,513. 12/1960 Fields ..260/523 3,284,492 1 1/1966 Fremery et a1. ..260/523 3,118,934 1/1964 Callighan et al ..260/523 Primary Examiner-Henry R. Jiles Assistant Examiner-R. S. Weissberg Attorney-Waters, Roditi, Schwartz & Nissen [57] ABSTRACT A method of producing l,8-naphtha1 dehyde monocarboxylic acid, characterized in that acenaphthylene is ozonized in the medium of a lower aliphatic alcohol, or in a mixture of a lower aliphatic alcohol with water, or in a mixture of an aliphatic ketone with water, in the presence of an alkaline earth metal hydroxide. The resulting reaction mass is treated with hydrochloric acid, the formed 1,8-naphthaldehyde monocarboxylic acid is separated from the alkaline earth metal hydroxide and washed to remove the traces of hydrochloric acid.

12 Claims, N0 Drawings METHOD OF PRODUCING 1,8- NAPHTHALDEHYDE MONOCARBOXYLIC bility and low volatility.

A method of producing 1,8-naph'thaldehyde dicarboxylic acid by ozonization of acenaphthylene is known. The process is carried out in the medium of carbon tetrachloride or butyl alcohol at temperatures below "zero. The reaction proceeds with the formation of explosion-hazardous peroxide products: alpoxy hydroperoxides, ozonides, polymer peroxides These peroxide products are separated and decomposed by special treatment during -12 hours with glacial acetic acid and potassium iodide, and the resulting 1,8-

' naphthaldehyde monocarboxylic acid is isolated with a yield of 49.9 wt. percent of the theoretical amount.

Said method is a multistage one, it proves to be technologically complicated, and is associated with the liberation of explosion-hazardous products, which limits the industrial uses of the above-discussed method. I v It is an object of the present invention to improve the method of producing 1,8-naphthaldehyde monocarboxylic acid by carrying out the ozonization of acenaphthylene-in such a'manner that the desired product'can be produced without the liberation of explosion-hazardous peroxide compounds, and thus to make the process fit for industrial uses.

Said object is accomplished by theprovision of a method. of producing 1,8-naphthaldehyde monocarboxylic acid by ozonizationof acenaphthylene, which, according to the invention, is carried out in a lower aliphatic alcohol, or in a mixture of a lower aliphatic alcohoi with water, or in a mixture .of a lower aliphatic ketone with water, in the'presence' of a hydroxide of an alkaline-earth metal, the latter being taken in an amount sufficient for the decomposition of peroxide compounds formed during the reaction. The reaction mass obtained after the ozonization is treated with hydrochloric acid to separate the resulting 1,8- naphthaldehyde monocarboxylic acid from the alkaline-earth metal hydroxide.

' and then, if necessary, recrystallized. The process is A carried out at room temperature and atmospheric pressure. The reaction is of a selective nature and proceeds.

according to the equation:

CO DOOH where Me is an alkaline-earth metal.

For a better decomposition of peroxide compounds formed in the course of ozonization of acenaphthylene, it is recommended that 0.5 to 1.5 parts by weight of an alkaline-earth metal hydroxide should be taken per 1 part by weight of acenaphthylene. As an the alkalineide.

The ozonization of acenaphthylene should be carried out in the medium of a lower aliphatic alcohol, such as ethyl, methyl, propyl or butyl alcohol, or in an aqueousalcoholic medium, that is, in a mixture of said alcohol with water. In the latter case the weight water-to-alcohol ratio of 1:10 is preferable; In case the ozonization is carried out in a water-ketone'mediurn, the weight ratio may be 1': 2-3 respectively. As the aliphatic ketone use may be made of acetone, methyl ethyl ketone, and other water-soluble ketones.

Usually the separated 1,8-naphthaldehyde monocarboxylic acid is washed with water, but any other appropriate solvent, such as butyl alcohol, may also be 7 used.

For obtaining a higher-purity'product, 1,8-naphth'aldehyde monocarboxylic acid is recrystallized from benzene or toluene. The temperature of the recrystallized productis l69-17'O C.

As can be seen from the'present specification, the herein proposed method of producing l,8- naphthaldehyde monocarboxylic acid is simple and safe for iridustrial realization, since explosion-hazardous com- 7 of an alkaline-earth metal. Therefore the stage of isolation of said explosion-hazardous compounds isobviated, and the'process isthus'simplified. Moreover,

. the present invention provides for an almost twofold illcrease in. the yield of the desired product, as compared with the method-known heretofore.

Given hereinbelow are illust'rativeexamples of carrying out the method of the invention.

Example 1 A reactor equipped with a stirrer, a condenser and a gas feed tube is charged with 20 g of acenaphthylene,

g of water 200 mlof acetone and 35 g of calcium hydroxide. Then oxygen containing 2 to 5 percent of ozone is passed through the resulting suspension under intensive stirring and at room temperature. No 'perox ideproducts are presentin the reaction'mixture, the

' content of active oxygen in weight percent'being zero.

The" precipitate is filtered, washed with "acetone to remove tra'c es of acenaphthylene, and dissolved in .a

weak solution of hydrochloric acid." The precipitated amount).

l,8-naphthaldehyde monocarboxylic acid is filtered,

(98 percent of the theoretical amount).

EXAMPLE 2 Acenaphthylene is ozonized as described in Example 1, but in the presence of 35 g of barium hydroxide. The reaction mixture istreated by following the procedure described in Example 1 Theyield of 1,8-naphthaldehyde monocarboxylic acid is 94 percent of I the A theoretical amount.

EXAMPLE 3 Acenaphthylene is ozonized as described in Example 1, but in the presence of 35g of magnesium hydroxide. The reaction mass is treated by following the procedure described in Example 1. The yield of 1,8maphthaldehyde monocarboxylic acid is 23 g (87 percent of thetheoretical amount).

' EXAMPLE 4 -.A reactor similar to that described in Example 1 is charged with 20g of acenaphthylene, 60 g of water,

200 ml of acetone;'then20 g of barium hydroxide are added thereto. Theozonization and treatment of the reaction products are carried out as described in Example 1 The yield of 1 ,8-naphthaldehydemonocarboxylic acid is 24.2 g (92'perce'nt of the theoretical amount).

EXAMPLE 5 A reactorsimilar to that described in Example 1 is 'charged with 20 g of acenaphthylene, 60 g of water, 200 ml of acetone, and 10 gof barium hydroxide. .The

ozonization and treatment of the, reaction products are carried out as described in Example 1. The yield of 1,8-

naphthaldehyde monocarboxylic-acid is 22.4 g'(85 percent of the theoretical amount).-

EXAMPLE 6 EXAMPLE 7 Acenaphthylene is ozonized as described in Example 6, but in the medium of 200 g of ethyl alcohol. The

yield of l,8-naphthaldehyde monocarboxylic acid is 21 r g (80 percent of the theoretical amount).

EXAMPLE s EXAMPLE9 Acenaphthylene is ozonized by following the procedure described in Example 6, but in the medium of 200 g of butyl alcohol. The yield of 1,8-naphthalthe theoretical amount).

EXAMPLE 10 A reactor similar to that described in Example 1 is charged with 20 g of acenaphthylene, 20 g of water,-

200 g of butyl alcoholand 20 g of calcium hydroxide Throughthe resulting suspension oxygen containing 5 percent of ozone is passedtill the ozone breakthrough.

The precipitate is filtered, washed with hot butyl alcohol to remove traces of acenaphthylene. Further treatment of the reactionproducts is carried out by following the procedure as described in Example 1. The yield. of l,8-naphthaldehyde monocarboxylic acid is 23.6 g percent of the theoretical amount).

What is claimed is;

1. A method of producing 1,8-naphthaldehyde monocarboxylic acid comprising ozonizing acenaphthylene room temperature and atmospheric pressure in the medium of a lower aliphatic alcohol, or in a mixture of said alcohol withwater, or in a mixture of a lower aliphatic ketone with water,in the presence of an alkaline earth metal hydroxide which is taken in an amount sufficient for the decomposition of those peroxide compounds which form during the reaction; treating the resulting reaction mass with hydrochloric acid to separate the formed l,8-naphthaldehyde tion of acenaphthylene is carried o'ut'in the presence of calcium hydroxide. j I I r 5. A method as claimed in claim l, wherein-ozonization of acenaphthylene is carried out in the presenceof magnesium hydroxide. I

6. A method as claimed in claim -1, wherein-the ozonization of acenaphthylene is carried out in a medi urn consisting of water and a lower aliphatic ketone,

said components being taken in a weight ratio of 1:2-3'.

wherein the lower 7. A method as claimed in claim 6, aliphatic ketone is acetone.

8. A method as claimed in claim 6, wherein aliphatic ketone is methyl-ethyl ketone.

9. A method asclaimed in claim 1, wherein the ozonization is carried out in an aqueous-alcoholic medium with the water-to-alcoh ol weight ratio being 1:10.

aliphatic alcohol is ethyl alcohol. f

11. A- method as claimed in claim 1, wherein the aliphatic alcohol is propyl'alcohol. 3 f

. 12. A'method as claimed in" claim 1, wherein aliphatic alcohol is butyl alcohol.

the

the lower 10. A method as claimed in claim l, where in the 

2. A method as claimed in claim 1, wherein 0.5-1.5 parts by weight of an alkaline-earth metal hydroxide are taken per part by weight of acenaphthylene.
 3. A method as claimed in claim 1, wherein the ozonization of acenaphthylene is carried out in the presence of barium hydroxide.
 4. A method as claimed in claim 1, wherein ozonization of acenaphthylene is carried out in the presence of calciUm hydroxide.
 5. A method as claimed in claim 1, wherein ozonization of acenaphthylene is carried out in the presence of magnesium hydroxide.
 6. A method as claimed in claim 1, wherein the ozonization of acenaphthylene is carried out in a medium consisting of water and a lower aliphatic ketone, said components being taken in a weight ratio of 1:2-3.
 7. A method as claimed in claim 6, wherein the lower aliphatic ketone is acetone.
 8. A method as claimed in claim 6, wherein the lower aliphatic ketone is methyl-ethyl ketone.
 9. A method as claimed in claim 1, wherein the ozonization is carried out in an aqueous-alcoholic medium with the water-to-alcohol weight ratio being 1:10.
 10. A method as claimed in claim 1, wherein the aliphatic alcohol is ethyl alcohol.
 11. A method as claimed in claim 1, wherein the aliphatic alcohol is propyl alcohol.
 12. A method as claimed in claim 1, wherein the aliphatic alcohol is butyl alcohol. 